Method for the coagulation of emulsion polymerizates



Dec. 7, 1948. w; w. WATERMAN ETAL- 23,455,714

METHOD FOR THE coAGULATIoN v 0F EMULsIoNPoLYMERIzATEs Filed Dec. 5. 1942 2 Sheets-S'heet 1 d I RccuLArek ulfasug/vc DRUM FROM , 'Ffa-4I' De@ 7, 1948- w.`w. WATERMAN ETAL '2,455,714

" 4 METHOD FCR THE COAGULATION f OF EMULS 10N POLYMERIZATES Filed Dec. 5, 1942 2 shams-sheet 2 nzpneszj; zzzLeAsf cas /2 u 2 all F/GQF g m mmf Patented Dec. 7, 1948 ME'rnon Foa'rna coAGULa'rIon or Eownsuon roLnrEmzA'ras wenden w. waterman, Cranford, ma meat o. Ohsol, Railway, N. J., assignors to Standard Oil Development Company, a corporation of Dela- Appucsuon December s, 1942, serial No. 461,960 4 claims. (ci. zoo-s45) This invention pertains to themanufacture of emulsion polymerizates and particularly to the manufacture of latices oi synthetic rubber-like materials.

It is the object of the present invention to provide the art with a novel process and apparatus for the treatment of emulsion polymerizates, particularly latices of synthetic rubber-like materials.

It is a further object of the present invention to provide the art with a method and apparatus for continuously repressuring latices of synthetic rubber-like materials preparatory to coagulating the same.

It is the object of this invention to provide a method whereby a latex of a synthetic `rubber like material and a liquid repressuring agent are continuously proportioned in a zone in which solution may take 'place at a. pressure which is higher than that at which coagulation occurs.

It isalso the object of this invention to provide a method whereby latices oi synthetic rubberlike materials and liquid repressuring agents are mixed under conditions of agitation and contact time such that there is rapid and sufficient solution of repressuring agent in the latex so that when the pressure is lowered, the latices will be saturated with Vthe liquid repressuring'agent atv lnitrile, methacrylic acid nitrile, acrylic and' methacrylic acid esters and unsaturated ketones such as methyl vinyl ketone and the like by polymerization in aqueous emulsion. 'Ihe polymerization reaction mixture is generally prepared by agitating the polymerizable materials in about double the quantity of water using a soap or other suitable emulsiiying agent. The polymerization is usually eiected at temperatures of about 30 to 60 C. and in the presence of a suitable polymerization catalyst which is capable of liberating oxygen under the polymerization conditions. Such catalysts include hydrogen peroxide,

valkali metal and ammonium persulfates or perborates or benzoyl peroxide or the like. The polymerization is continued until about 50 to- 85% of the monomeric materials are polymerized, whereupon the polymer emulsion or latex is .coagulated in order to obtain the polymer in solid form.

Considerable diiliculty vhas been encountered in finding a suitable method for coagulating euch latices.

ing suflcient acid such as acetic, formic, hydrochloric or sulfuric acids to decompose the soap or by adding an inorganic salt in suiilcient amount to salt out the dispersed polymer. However, decomposition with acid is not satisfactory because the fatty acid from the soap remains inthe coagulated polymer and can only be removed by extraction with organic solvents. Furthermore the coagulate obtained tends to asglomerate to a coherent mass which must be subjected to a masticationor attritioning treatment in order effectively to wash the polymer. Coagulation by salting out, while it may bring down relatively small particles ol coagulate, does not overcome these-diiiiculties since the soap emulsier is also coagulated' with the polymer and must be washed therefrom. v

As disclosed in application Berial No. 365,012 of Vanderbilt and Beckley, filed November 9, i940, now U. S. Patent 2,385,172, the size oi the coagulated particles can be regulated by pl-l control. It is possible thereby to adjust this particle size so that the material can be readily ltered by means ofrotary-vacuum or iilter-press type lters. The particles can also be obtained suiilciently small so that the emulsifier and other water soluble materials can be'nearly completely removed by simple leaching with water.` dlthough this method of coagulating is especially applicable when using Water-soluble soaps as emulsiers, it is also advantageously used when the emulsifler consists of salts of sulfatcd alcoh ols, alkylated naphthalene sulfonates, alkyl amine salts, and the like. The coagulate thus obtained is `usually separated from the salty liquor by means of a rotary suction filter and in view of the dilculties encountered in washing the resultant lter cake, it is desirable to redisperse it in water and contact it with water lfor about 10 to 30 minutes whereupon it is again filtered and washed with water to remove the adhering liquid, as disclosed in Serial No. 413,582, Waterman and Ohsol, filed October 4, '1941.

It has been found that when latices of syn- When water-soluble soaps are used as emulsifier coagulation has been effected by add- Y Y it is highly desirable if not absolutely essential to prepare latices of synthetic rubber-like materials of a Williams plasticity i60-30 or even lower -in order that they may be satisfactorily compounded and processed in subsequent operations, it was found impossible to coagulate such latices and to iilter and wash the coagulate with the conventional type equipment.

As disclosed in application Serial No. 407,476, iiled Augustl9, 1941, now U. S. Patent 2,393,348 by Waterman and Vanderbilt, it has been found that if the coagulation of latices of synthetic rubber-like materials having Williams plasticities of less than 175-75 is conducted in the presence of a small, somewhat critical, proportion of low boiling hydrocarbon, such'as butadiene or the like, a much smaller amount of coagulant is required and the coagulate is thrown down in a much more granular and less sticky form than is obtained in the absence of the hydrocarbon. Also, the coagulate may be obtained in relatively uniform particles, of any desired size, which are particularly easy to wash free from catalyst, emuisifler, coagulant and other water-soluble impurities. By this process, latices of synthetic rubber-like materials having al Williams plasticity as low as 50-0 can be coagulated, illtered,` reslurried in water and again filtered without the cagulated particles adhering together. While the latex upon completion of the polymerization contains some unreacted butadiene, this can not ordinarily be retained until the coagulation step because of the necessity of stripping unreacted monoolenicmaterials such as acrylonitrile and the like from the latex. Since this stripping operation removes all of the unpolymerized butadiene or other diolefin, it is necessary to repressure the latex by the addition 'of fresh dioleiin or other low boiling hydrocarbon.

The present invention is an improvement of the foregoing process in as much as it permits the repressuring of latices to be carried out in a continuous manner. It is. of course, highly desirable to conduct these operations continuously not only in order to obtain a greater production 4volume but also to obtain a more uniform product through the maintenance of constant conditions at each processing zone. It is generally characteristic of continuous operation of this type that considerably less supervision is necessary than is required in batch operations of equal volume. Also, by maintaining continuous flow of slurry through the equipment, less chance is .given for the polymer to settle out and plug lines,

valves or pumps. Also, the formation of deposits in the vessels themselves due to alternate wetting and drying of the surfaces as is unavoidable in batch operation are avoided in the continuous process of the present invention.

Apparatus suitable for the conduct of the process in accordance with the present invention is illustrated diagrammatically in the accompanying drawing. In the drawing,

Figure I shows an apparatus for continuously repressuring latices wherein the represented latexis passed through a separate ilash drum and the flow of repressuring agent into the repressuring drum is controlled .by the ilow of release gas from the ilash drum.

Figure II is a similar apparatus but in which in lieu of a separate flash drum the coagulator is used as a combined coagulator and flash drum.

Figure III is an arrangement similar to Figure I but wherein the rate oi repressuring agent supply is controlled bythe difference in pressure between the repressuring drum and the ilash drum.

Figure IV is a further modification wherein the ilow oi' repressuring agent into the repressuring drum is controlled by the pressure in this drum.

Figure V shows an arrangement wherein a proportioning pump is used to supply repressuring liquid at a rate controlled by the latex supply.

In the several figures oi' the drawing I is the repressuring vessel wherein the repressuring agent is dissolved in the latex and 2 is the line for supplying stripped latex. 3 is the line for supplying low boiling `hydrocrabon repressuring agent to the repressuring vessel and 4 is an agitator for mixing or emulsifying the added hydrocarbon in the latex. The latex is discharged from the dissolving vessel through line 5 and valve 8 which is controlled by the liquid level in vessel I. The pressure in vessel I is equal to or greater than the vapor pressure of the repressuring hydrocarbon supplied through 3. The latex discharged through valve 8 is passed into the holding tank 'i and thence into vessel 8 wherein the pressure is allowed to fall to the desired value prior to discharge to a suitable coagulating vessel. The hydrocarbon released in vessel 8 in discharged through line 9 and a suitable pressure controller such as a spring loaded back pressure valve III.

It is preferred that the amount of excess repressuring agent released through valve IIl be utilized to control automatically the amount of liquid repressuring agent supplied to vessel I. This can be accomplished by providing an oriiice or ilow meter I I on release line 8 the pressure drop across which operates to reset a iiow controller I2 on the liquid repressuring agent supply line 3 in such a way that an increased flow of gas causes a decreased ilow oi liquid and a decreased flow of gas causes an increased ilow of liquid repressuring agent. The vented repressuring agent is passed to a recovery system wherein it is reconditioned for reuse in the process. If the agitation and holdup time in repressuring drum is sufficient to establish the desired degree of solution, holding drum 1 may be omitted. or by-passed by closing valves I5 and I8 and opening valve I1.

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The vented latex is discharged from vessel 8 through line I3 and valve I4 which is controlled by the liquid level in vessel 8. I'he repressured latex discharged through line I3 is then ready for coagulation, washing and drying in any suitable equipment.

The arrangement shown in Figure n is essentially the same as that of Figure I except thr the flash drum lis made to serve the dual function of flash drum and coagulator by providing the same with a mechanically driven agitator I8 arranged in a draft tube I9. A line 20 provided with a ilow controller 2| supplies brine to the`V` vessel 8. As shown, the brine and the latex supply pipes discharge into the draft tube or at a point of maximum agitation. In this arrangement also, the iiow oi' released repressuring agent through a ow meter I l a release line 9 is utilized to control the flow of repressuring agent to the repressuring drum.

Figure III shows an arrangement wherein the rate of butadiene supply to the repressuring drum is controlled by the diiferenc'e in pressure between the repressuring drumand the iiash drum. In this ligure a did'erential pressure controller 22 is connected to the repressuring drum l and the 'dash drum 8. Since the pressure in dash drum 8 is maintained substantially constant by the pressure controller on the release line l, the-differential pressure controller 22 is essentially actuated by variations in pressure in repressuring drum i, a drop in the pressure diierential actuating the controller 22 so that an increase of liow of repressuring agent to drum l is permitted while f an increase in the. pressure dlierential causes a decrease in therlow of repressuring agent.

In Figure IV the rate of butadiene supply to the repressurlng drum is, controlled by the pressure in drum i, an increase in the pressure causing a reduction in the supply oiv repressuring agent and vice versa.

In Figure V, a proportioning pump 23 is p'rovided in the repressuring agent supply line 3. A. Venturi meter or the like 24 is provided in the laten supply line :2 and the rate of flow oi latex through the ilovv` meter 24 is utilized to control thel operation of the proportioning pump 2t. The ratio between repressuring agent and laten is manually adjusted on the basis of the amount of releasegas indicated by the flow meter it.

The coagulant solution supplied to the drum t through line 2B and iiow 'controller 2|. As described above. the coagulator is preferably provided with a draft tube and propeller in order to obtain complete contact of the latex with the coagulant solution. TheV control setting of the rate of coagulant solution ow could be adjusted automatically, if desired by a reset operated by a. flow meter on the latex supply line, or by the use of another proportioning pump.

The coagulated slurry is discharged from drum ,d through liquid level control valve i4 and is passed into a release drum 21 which is maintained under a vacuum in order to flash oil and permit recovery of the butadiene or other repressuring agent in the coagulated slurry. The release drum is operated at as low a pressure as is economicalto use. based on the value of the material to be recovered or safety hazzards involved. A pressure of about 2# absolute has been found to be quite suitable. The dashed oil' repressuring agent is withdrawn through pressure regulator 2E on line 29 and is passed to suitable compressors for reconditioning the same for reuse in the process. The stripped latex is discharged from the release drum through liquid level controlled valveA and passes to suitable filtering, washing and drying equipment.

In view of the tendency for the latex or th coagulated slurry to adhere to the surfaces with which it'comes into contact, it is highly desirable to utilize valves of a special or streamlined design in all linesthrough which the latex or coagulate passes. Insuch valves, the spindle lifts clear of the throat and the liquid enters at right angles to the axis of the valve. y

A typical .operation of our process and apparatus is as follows:

An emulsion polymerizate is prepared by emulsifying a mixture of '75 parts butadiene and 25 parts of acrylonitrile in about. 200 parts ofy water using about 6 parts of sodium oleate as emulsiiier and Vpolymerizing in the presence of about 0.1` to about 8 parts of ammonium persulfate and about 3 to 5 parts of a modifying agent,4 such as dodecyl mercaptan at about 30 C. for about 12 hours. Y' Upon completion of the polymerization and pre-erably after the addition of a stabilizer such as phenyl-B-napthylaxnine.A the latex is stripped of unreacted polymerizable material by flashing ci! butadiene and subjecting the latex to vacuum distillation if desired with steam in order to remove unreacted acrylonltrile.` The resultant stripped and stabilized latex is cooled and introduced into the dissolving vessel I at about C. and at a rate of about 20 gallons per minute. Liquid butadiene is supplied through line 3 at about 0.5 gallon per minute and the mixture level-controlled rvalve 6 into holding tank 1 in which the latex is retained for a time sutilcient for enough of the repressurlng agent to dissolve in the aqueous and non-aqueous phases of the latex so that when the pressure is allowed to fall to the desired value in vessel 8, the vapor phase will be in equilibrium with the liquid with respect to Athe quantity of -repressuring agent in solution.

The rate oi establishment of this degree of solution, depending upon the eiilciency of emulsiilcation in vessel I, may be sufliciently rapid that the holding tank 1 may be omitted. In this case the valves Ill and I6 are closed and valve i1 is opened permitting the latex topass directly from vessel i to vessel 8.

'I'he pressure in vessel is about 5 lbs/sq. in., i. e. substantially below the vapor' pressure of butadiene under the temperature prevailing,

therein, the pressure being that found to be in equilibrium with the latex containing the desired amount oi dissolved butadiene. A greater or less pressure may be maintained. depending upon whether more or less butadiene is desired in the latex. Greater amounts of butadiene cause the formation of more granular, nner' coagulates,

while smaller amounts cause the formation oi'4 lmore tacky coagulates oi.' larger particle size.

T'he excess butadiene vaporized in vessel 8 escapes through the pressure control valve il and prei-v erably flows through an oriice which measures the iiow of lrejected butadiene, and can be used as a basis foradjusting the rate of liquid butadiene addition to vessel i. The repressured latex is dischargedtrom the vessel 8 and may thereupon be continuously coagulated with brine or other suitable coagulant. y

The latices that are repressured in accordance with the instant invention usually contain from about 0.5 to about 5% of repressurlng agent and' are capable or being coagulated with y smaller amounts oi' coagulant and yield a coagulate that 'is less tacky and more granular in nature and may therefore be easily washed completely free of soluble contaminants.

While butadiene has been mentioned above and is in fact the preferred repressuring agent. it is to be understood that other low boiling hydrocarbons such as propane. propylene, isobutylene, normal butylenes, isoprene and the like taining a single C==C linkage such as acrylic acid nitrile, methacrylic acid nitrile, styrene, substituted styrenes, acrylic and methacrylic acid esters and methyl vinyl ketone.

What we claim and desire to secure by Letters Patent is:

1. The process which comprises continuously combining a latex, obtained by the polymerizationv in aqueous emulsion oi' a reaction mixture of butadiene and acrylonitrile and which has been substantially freed from monomers, with an excess of butadiene as repressuring agent, mixing the latex and repressuring agent under a pressure y at least equal to the vapor pressure of said repressuring agent to eilect suilicient solution of the repressuring agent in the aqueous and nonaqueous phases of the latexto render the latex substantially saturated with repressuring agent at the lower pressure next applied, continuously discharging the treated latex into a ilashlng zone of lower pressure, venting oi! the liberated excess repressuring agent, controlling the rate of admission of the repressuring agent so as to maintain a substantially Yconstant diierential pressure between the mixing zone and the flashing zone, maintaining a substantially constant pressure in the flashing zone by regulating the rate at which the liberated excess repressuring agent is vented oil and continuously adding coagulant brine to the treated latex while the latex con- .tains from about 0.5 to of repressuring agent.

.the repressuring agent in the aqueous and nonaqueous phases of the latex to render the latex substantially saturated with repressuring agent at the lower pressure next applied, continuously discharging the treated latex into a ilashing zone of a lower pressure, venting off the liberatedexcess repressuring agent, controlling the rate of admission of the repressuring agent so as to maintain a substantially constant pressure in the mixing zone, independently'maintaining a. substantially constant pressure in the ashing zone by regulating the rate at which the liberated excess repressuring agent is vented oil? and continuously adding coagulant brine to the treated latex while the latex contains from about 0.5 to 5% of repressuring agent.

3. In a method for coagulating latices obtained by the copolymerization in aqueous emulsion of a conjugated diolen of from 4 to 6 carbon atoms per molecule, and an unsaturated comonomer containing a single CH2=C group, which latices have been substantially freed of unreacted monomers. the steps` which comprise continuously` combining said latices with an excess o! butadiene as repressuring agent, mixing the latices and repressuring agent under a pressure at least equal to the vapor pressure of said repressuring agent to eect suiiicient solution of repressuring agent in the aqueous and non-aqueous phases of the latex to render the latex substantially saturated with repressuring agent at the lower pressure next applied, continuously discharging the treated latex into a zone oi.' lower pressure, conbeen substantially freed oi' unreacted monomers,

' the steps which comprise continuously combining said latices with an excess of butadiene as repressuring agentt mixing the latices and repressuring agent under a pressure atleast equal to the vapor pressure of said repressuring agent to eect sumcient solution of repressuring agent in the aqueous and non-aqueous phases of the latex to render the latex substantially saturated with repressuring agent at the lower pressure next applied, continuously discharging the treated latex into a zone oi' .lower pressure, continuously venting oil.' repressuring agent released from said latices thereby reducing the repressuring agent content of, the latex to from 0.5 to 5% and coagulating the latex containing said amounts of repressuring agent by adding coagulant brine thereto.

WENDELL W. WATERMAN.

ERNEST O. OHSOL.

REFERENCES CITED The following references are of record in the ille of this patent:

UNITED STATES PATENTS Number Name Date 2,085,524 De Simo June 29, 1937 2,229,661 Mann Jan. 28, 1941 2,269,421 Arveson I Jan. 13, 1942 2,393,348 Waterman Jan. 22, 1946 FOREIGN PATENTS Number Country Date 304,207 Great Britain Apr. 15, 1930 312,201 Great Britain May 2l, 1929 

